CN114643072B - Preparation method of metal single-atom modified three-dimensional porous MXenes composite material - Google Patents
Preparation method of metal single-atom modified three-dimensional porous MXenes composite material Download PDFInfo
- Publication number
- CN114643072B CN114643072B CN202111401690.8A CN202111401690A CN114643072B CN 114643072 B CN114643072 B CN 114643072B CN 202111401690 A CN202111401690 A CN 202111401690A CN 114643072 B CN114643072 B CN 114643072B
- Authority
- CN
- China
- Prior art keywords
- dimensional porous
- metal
- composite material
- modified
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002135 nanosheet Substances 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 41
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 238000000137 annealing Methods 0.000 claims description 26
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 17
- 238000004108 freeze drying Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002064 nanoplatelet Substances 0.000 claims description 4
- 229910052755 nonmetal Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- PPVRVNPHTDGECD-UHFFFAOYSA-M F.[Cl-].[Li+] Chemical compound F.[Cl-].[Li+] PPVRVNPHTDGECD-UHFFFAOYSA-M 0.000 claims description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- 239000011363 dried mixture Substances 0.000 claims 2
- 150000002843 nonmetals Chemical class 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 5
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 48
- 239000012265 solid product Substances 0.000 description 24
- 238000012512 characterization method Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000001228 spectrum Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 230000005540 biological transmission Effects 0.000 description 14
- 238000000089 atomic force micrograph Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 8
- 230000004075 alteration Effects 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- -1 transition metal carbides Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910021076 Pd—Pd Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a controllable preparation method of a three-dimensional porous MXenes composite material modified by metal monoatoms. The composite material prepared by the invention takes a three-dimensional porous bimetal doped MXenes nano sheet as a substrate, and doped metal elements are anchored on the nano sheet in a form of single atoms. Meanwhile, the preparation method is simple, quick and efficient, has universality and can prepare a series of three-dimensional porous MXees composite materials modified by different metal monoatoms.
Description
Technical Field
The invention belongs to the field of preparation of monoatomic catalytic materials, and particularly relates to a preparation method of a metal monoatomic modified three-dimensional porous MXenes composite material.
Background
MXenes is a novel two-dimensional nanomaterial comprising transition metal carbides, nitrides and carbonitrides thereof, and has a general formula of M n+1XnTx, wherein M is a pre-transition metal element (Sc, ti, V, cr, zr, nb, mo, hf, ta and the like), X is C, N or CN, T x is a surface functional group (-OH, -F, =O and the like), and n is 1,2 and 3. The unique two-dimensional layered structure and the surface chemical composition formed by the conductive carbon layer and the metal layer endow the MXees material with excellent conductivity, mechanical property, hydrophilic property and ion transmission property, so that the MXees has great application prospect in the field of electrocatalysis. The surface functional groups of mxnes are the primary active sites in the electrocatalytic reaction. However, the intermediate binding energy of the surface functional groups is extremely high, resulting in very slow kinetics of mxnes during electrocatalysis. Thus, research into electrocatalytic materials based on mxnes remains a great challenge. In addition, as with graphene and other two-dimensional materials, spontaneous stacking and agglomeration can be generated between MXenes nano-sheets due to strong van der Waals force interaction, which seriously affects the effective exposure of the catalytic active sites and restricts the practical application of the MXenes nano-sheets. Currently researchers are working on improving the activity of mxnes electrocatalytic materials by surface chemical composition modification, with the most widely studied metal monoatomic doping strategy. However, previous studies have ignored the prevention of spontaneous stacking and agglomeration of mxnes sheets by constructing a three-dimensional porous structure, improving the mass transfer capacity and stability of mxnes electrocatalytic materials, and thus improving their overall electrocatalytic performance. Therefore, there is an urgent need to develop a method for preparing a metal monoatomically modified three-dimensional porous mxnes composite material.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a preparation method of a metal single-atom modified three-dimensional porous MXenes composite material.
The invention relates to a metal monoatomic modified three-dimensional porous MXenes composite material, which is characterized by comprising the following components:
The metal monoatomic modified three-dimensional porous MXenes composite material is characterized by having an irregular three-dimensional porous microstructure, and the pore diameter of the three-dimensional porous microstructure is about 5-20 microns; the metal monoatoms are uniformly distributed on the MXees substrate with a three-dimensional porous structure, and the size of the metal monoatoms is in a sub-nanometer scale.
Further, the MXenes include, but are not limited to, ti 3C2TX、Ti2CTX、Mo2CTX, ti 3C2TX、Ti2CTX、Mo2CTX, preferably Ti 3C2TX.
Further, the metal monoatoms include Pt, ir, ru, pd, au, but are not limited to Pt, ir, ru, pd, au, preferably Pt.
Further, the metal monoatoms are anchored on the MXees substrate with a three-dimensional porous structure through chemical bonds formed by non-metal heteroatoms N and P (or S).
The preparation method of the three-dimensional porous MXenes composite material modified by metal monoatoms comprises the following steps:
s1, chemically stripping the Ti 3AlC2 material by adopting a lithium fluoride-hydrochloric acid mixed solution to obtain a few-layer Ti 3C2TX nano-sheet solution.
S2, sequentially adding melamine, triphenylphosphine (or thiourea) and corresponding metal precursors to be doped into the less-layer Ti 3C2TX nano-sheet solution, and then freeze-drying the mixture.
And S3, annealing the mixture obtained after freeze drying under normal pressure in an argon atmosphere, cooling to room temperature after annealing is completed, and collecting a reaction product to obtain the metal monoatomic modified three-dimensional porous MXees composite material.
According to the scheme, the triphenylphosphine in the step S2 needs to be dissolved in tertiary butanol first and then is sonicated for 30-60 minutes.
According to the scheme, the mass ratio of the Ti 3C2TX nano-sheets to the melamine in the step S2 is 1:1-1:3, and the mass ratio of the Ti 3C2TX nano-sheets to the triphenylphosphine (or thiourea) is 1:1-1:3.
According to the scheme, the annealing temperature in the step S3 is 400-600 ℃, and the annealing time is 1-4 hours.
Compared with the prior art, the invention has the following outstanding advantages:
(1) The invention smartly anchors the metal monoatoms on the MXees material with three-dimensional porous structure, and the metal monoatoms are precisely coordinated with the hetero atoms N and P (or S).
(2) The preparation method disclosed by the invention has universality and can be used for preparing a series of metal single-atom modified three-dimensional porous MXenes composite materials.
(3) The preparation method is simple, quick and efficient, and is easy to realize large-scale and industrialized production.
Drawings
FIG. 1 is a material characterization of a few-layer Ti 3C2TX nanoplatelet in an example. FIG. 1a is a High Resolution Transmission Electron Microscope (HRTEM) image of Ti 3C2TX nanoplatelets. FIG. 1b is an Atomic Force Microscope (AFM) image of a Ti 3C2TX nanosheet. As shown by AFM, the thickness of the Ti 3C2TX nano-sheets is about 3-5 nanometers.
FIG. 2 is a material characterization of the Pt single atom modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite of example 1. FIG. 2a is an X-ray diffraction pattern (XRD) pattern of a three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX (PNPM) and Pt single atom modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite (Pt SA-PNPM). Fig. 2b is a Scanning Electron Microscope (SEM) image of a Pt monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite. FIG. 2c is a scanning transmission microscope high angle annular dark field image (HAADF-STEM) of a Pt monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite. FIG. 2d, e is an X-ray photoelectron spectroscopy (XPS) of a Pt monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite. FIG. 2f is a Fourier transform extended X-ray absorption fine structure (FT-EXAFS) spectrum of a Pt monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite at Pt L 3 -edge.
FIG. 3 is a material characterization of the Ir monatomic modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite of example 2. Fig. 3a is a scanning transmission microscope high angle annular dark field image (HAADF-STEM) of an Ir monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite. FIG. 3b is a Fourier transform extended X-ray absorption fine structure (FT-EXAFS) spectrum of an Ir monatomic modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite at Ir L 3 -edge.
FIG. 4 is a material characterization of the Ru monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite of example 3. Fig. 4a is a scanning transmission microscope high angle annular dark field image (HAADF-STEM) of a Ru monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite. FIG. 4b is a Fourier transform extended X-ray absorption fine structure (FT-EXAFS) spectrum of a Ru monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite at Ru K-edge.
FIG. 5 is a material characterization of the Pd monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite in example 4. Fig. 5a is a scanning transmission microscope high angle annular dark field image (HAADF-STEM) of a Pd monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite. FIG. 5b is a Fourier transform extended X-ray absorption fine structure (FT-EXAFS) spectrum of a Pd monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite at Pd K-edge.
FIG. 6 is a material characterization of the Au single atom modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite of example 5. FIG. 6a is a scanning transmission microscope high angle annular dark field image (HAADF-STEM) of an Au monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite. FIG. 6b is a Fourier transform extended X-ray absorption fine structure (FT-EXAFS) spectrum of an Au monatomic modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite at Au L 3 -edge.
FIG. 7 is a material characterization of the Ir monatomic modified three-dimensional porous nitrogen sulfur doped Ti 3C2TX composite of example 6. FIG. 7a is a scanning transmission microscope high angle annular dark field image (HAADF-STEM) of an Ir monoatomically modified three-dimensional porous nitrogen-sulfur doped Ti 3C2TX composite. Fig. 7b and c are X-ray photoelectron spectroscopy (XPS) diagrams of a three-dimensional porous nitrogen-sulfur doped Ti 3C2TX composite modified with Ir monoatoms. FIG. 7d is a Fourier transform extended X-ray absorption fine structure (FT-EXAFS) spectrum of an Ir monatomic modified three-dimensional porous nitrogen-sulfur doped Ti 3C2TX composite at Ir L 3 -edge.
The specific embodiment is as follows:
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1
Preparation of a Pt single-atom modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material (abbreviated as Pt SA-PNPM):
Firstly, 1.2 g of lithium fluoride is added into 9mol/L hydrochloric acid solution, and the mixture is stirred and mixed uniformly. 1 g of Ti 3AlC2 was then added to the above solution in portions. After stirring for 1 hour until the mixture was uniform, the mixed solution was transferred to a thermostatic water bath, and the reaction temperature and time were set at 35℃and 24 hours. After the reaction is finished, centrifugally collecting a solid product after the reaction, washing the solid product to be close to neutral by deionized water, and centrifugally collecting the washed solid product. Adding deionized water into the solid product, carrying out ultrasonic treatment for 1 hour under the protection of argon and ice water bath, centrifuging and collecting supernatant to obtain Ti 3C2TX nanometer sheet solution (about 5 mg/mL), wherein the centrifuging speed and the centrifuging time are set to 5000r/min and 1 hour. The TEM image of Ti 3C2TX nano-sheets is shown in fig. 1a and the AFM image is shown in fig. 1b, and it can be seen from the AFM image that the thickness of Ti 3C2TX nano-sheets is about 3.5 nm.
10Ml of the Ti 3C2TX nanometer sheet solution is taken, 100 mg of melamine and 100 mg of triphenylphosphine are added in sequence, and the mixture is stirred until the mixture is uniform.
And adding a hexahydrated chloroplatinic acid solution into the solution, controlling the mass ratio of Pt to Ti 3C2TX nano-sheets to be 3%, and stirring for 30 minutes by using a magnetic stirrer to uniformly mix the solution.
And freeze-drying the mixed solution.
And (3) annealing the mixture obtained by freeze drying in a tube furnace at normal pressure, wherein the annealing temperature and time are set to 500 ℃ and 2 hours by adopting argon protection. And after the annealing is finished, cooling to room temperature, and collecting a product to obtain the Pt single-atom modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material.
XRD characterization showed that the Pt monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite did not exhibit a significant diffraction peak for metallic Pt, indicating that Pt was distributed in a monoatomic state on the three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX (see fig. 2 a). Meanwhile, no obvious Pt nano particles appear in an SEM image of the Pt single-atom modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material (see FIG. 2 b).
Characterization of Pt monoatomic modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite using a spherical aberration correcting scanning transmission electron microscope, high power HAADF-STEM images (see fig. 2 c) showed that Pt monoatoms were uniformly distributed on three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX. X-ray photoelectron spectroscopy (XPS) showed that Pt atoms were anchored to the Ti 3C2TX substrate by forming chemical bonds with N and P heteroatoms (see FIG. 2d, e). X-ray absorption fine spectrum characterization is carried out on the three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material modified by Pt monoatoms, and the FT-EXAFS spectrum (see figure 2 f) has only coordination peaks of Pt, N and P and no Pt-Pt metal coordination peak, so that the existence of Pt in a monoatomic form is further proved.
Example 2
Preparation of an Ir monatomic modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material (abbreviated as Ir SA-PNPM):
Firstly, 1.2 g of lithium fluoride is added into 9mol/L hydrochloric acid solution, and the mixture is stirred and mixed uniformly. 1 g of Ti 3AlC2 was then added to the above solution in portions. After stirring for 1 hour until the mixture was uniform, the mixed solution was transferred to a thermostatic water bath, and the reaction temperature and time were set at 35℃and 24 hours. After the reaction is finished, centrifugally collecting a solid product after the reaction, washing the solid product to be close to neutral by deionized water, and centrifugally collecting the washed solid product. Adding deionized water into the solid product, carrying out ultrasonic treatment for 1 hour under the protection of argon and ice water bath, centrifuging and collecting supernatant to obtain Ti 3C2TX nanometer sheet solution (about 5 mg/mL), wherein the centrifuging speed and the centrifuging time are set to 5000r/min and 1 hour. The TEM image of Ti 3C2TX nano-sheets is shown in fig. 1a and the AFM image is shown in fig. 1b, and it can be seen from the AFM image that the thickness of Ti 3C2TX nano-sheets is about 3.5 nm.
10Ml of the Ti 3C2TX nanometer sheet solution is taken, 100 mg of melamine and 100 mg of triphenylphosphine are added in sequence, and the mixture is stirred until the mixture is uniform.
And adding chloroiridium hexahydrate solution into the solution, controlling the mass ratio of Ir to Ti 3C2TX nano-sheets to be 3%, and stirring for 30 minutes by using a magnetic stirrer to uniformly mix the solution.
And freeze-drying the mixed solution.
And (3) annealing the mixture obtained by freeze drying in a tube furnace at normal pressure, wherein the annealing temperature and time are set to 500 ℃ and 2 hours by adopting argon protection. And after the annealing is finished, the temperature is reduced to room temperature, and the product is collected, so that the Ir single-atom modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material can be obtained.
Characterization of the Ir monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite using a spherical aberration correcting scanning transmission electron microscope, high magnification HAADF-STEM images (see fig. 3 a) indicated that monoatomic Ir was uniformly distributed on the three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX. The three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material modified by Ir monoatoms is subjected to X-ray absorption fine spectrum characterization, and the FT-EXAFS spectrum (see figure 3 b) has only coordination peaks of Ir and N and P, and does not have Ir-Ir metal coordination peaks, so that the Ir is further proved to exist in a monoatomic form.
Example 3
Preparation of Ru single-atom modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material (abbreviated as Ru SA-PNPM):
Firstly, 1.2 g of lithium fluoride is added into 9mol/L hydrochloric acid solution, and the mixture is stirred and mixed uniformly. 1 g of Ti 3AlC2 was then added to the above solution in portions. After stirring for 1 hour until the mixture was uniform, the mixed solution was transferred to a thermostatic water bath, and the reaction temperature and time were set at 35℃and 24 hours. After the reaction is finished, centrifugally collecting a solid product after the reaction, washing the solid product to be close to neutral by deionized water, and centrifugally collecting the washed solid product. Adding deionized water into the solid product, carrying out ultrasonic treatment for 1 hour under the protection of argon and ice water bath, centrifuging and collecting supernatant to obtain Ti 3C2TX nanometer sheet solution (about 5 mg/mL), wherein the centrifuging speed and the centrifuging time are set to 5000r/min and 1 hour. The TEM image of Ti 3C2TX nano-sheets is shown in fig. 1a and the AFM image is shown in fig. 1b, and it can be seen from the AFM image that the thickness of Ti 3C2TX nano-sheets is about 3.5 nm.
10Ml of the Ti 3C2TX nanometer sheet solution is taken, 100 mg of melamine and 100 mg of triphenylphosphine are added in sequence, and the mixture is stirred until the mixture is uniform.
Ruthenium trichloride solution was added to the above obtained solution, the mass ratio of Ru to Ti 3C2TX nanosheets was controlled to 3%, and the solution was stirred with a magnetic stirrer for 30 minutes to mix the solution uniformly.
And freeze-drying the mixed solution.
And (3) annealing the mixture obtained by freeze drying in a tube furnace at normal pressure, wherein the annealing temperature and time are set to 500 ℃ and 2 hours by adopting argon protection. And after the annealing is finished, cooling to room temperature, and collecting a product to obtain the Ru single-atom modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material.
Characterization of the Ru monoatomic modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite using a spherical aberration correction scanning transmission electron microscope, high-power HAADF-STEM image (see FIG. 4 a) shows that Ru monoatoms are uniformly distributed on the three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX. The Ru monoatomic modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material is subjected to X-ray absorption fine spectrum characterization, and the FT-EXAFS spectrum (shown in figure 4 b) has only the coordination peaks of Ru, N and P and no Ru-Ru metal coordination peak, so that the Ru is further proved to exist in a monoatomic form.
Example 4
Preparation of Pd monatomic modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite (abbreviated as Pd SA-PNPM):
Firstly, 1.2 g of lithium fluoride is added into 9mol/L hydrochloric acid solution, and the mixture is stirred and mixed uniformly. 1 g of Ti 3AlC2 was then added to the above solution in portions. After stirring for 1 hour until the mixture was uniform, the mixed solution was transferred to a thermostatic water bath, and the reaction temperature and time were set at 35℃and 24 hours. After the reaction is finished, centrifugally collecting a solid product after the reaction, washing the solid product to be close to neutral by deionized water, and centrifugally collecting the washed solid product. Adding deionized water into the solid product, carrying out ultrasonic treatment for 1 hour under the protection of argon and ice water bath, centrifuging and collecting supernatant to obtain Ti 3C2TX nanometer sheet solution (about 5 mg/mL), wherein the centrifuging speed and the centrifuging time are set to 5000r/min and 1 hour. The TEM image of Ti 3C2TX nano-sheets is shown in fig. 1a and the AFM image is shown in fig. 1b, and it can be seen from the AFM image that the thickness of Ti 3C2TX nano-sheets is about 3.5 nm.
10Ml of the Ti 3C2TX nanometer sheet solution is taken, 100 mg of melamine and 100 mg of triphenylphosphine are added in sequence, and the mixture is stirred until the mixture is uniform.
And adding a potassium hexachloropalladate solution into the solution obtained above, controlling the mass ratio of Pd to Ti 3C2TX nano-sheets to be 3%, and stirring for 30 minutes by using a magnetic stirrer to uniformly mix the solution.
And freeze-drying the mixed solution.
And (3) annealing the mixture obtained by freeze drying in a tube furnace at normal pressure, wherein the annealing temperature and time are set to 500 ℃ and 2 hours by adopting argon protection. And after the annealing is finished, cooling to room temperature, and collecting a product to obtain the Pd single-atom modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material.
Characterization of Pd monoatomically modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite using a spherical aberration correcting scanning transmission electron microscope, high-power HAADF-STEM image (see FIG. 5 a) shows that monoatomic Pd is uniformly distributed on three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX. The three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material modified by Pd monoatoms is subjected to X-ray absorption fine spectrum characterization, and the FT-EXAFS spectrum (see figure 5 b) has only coordination peaks of Pd, N and P, and no Pd-Pd metal coordination peak, so that the Pd is further proved to exist in a monoatomic form.
Example 5
Preparation of Au single-atom modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material (abbreviated as Au SA-PNPM):
Firstly, 1.2 g of lithium fluoride is added into 9mol/L hydrochloric acid solution, and the mixture is stirred and mixed uniformly. 1 g of Ti 3AlC2 was then added to the above solution in portions. After stirring for 1 hour until the mixture was uniform, the mixed solution was transferred to a thermostatic water bath, and the reaction temperature and time were set at 35℃and 24 hours. After the reaction is finished, centrifugally collecting a solid product after the reaction, washing the solid product to be close to neutral by deionized water, and centrifugally collecting the washed solid product. Adding deionized water into the solid product, carrying out ultrasonic treatment for 1 hour under the protection of argon and ice water bath, centrifuging and collecting supernatant to obtain Ti 3C2TX nanometer sheet solution (about 5 mg/mL), wherein the centrifuging speed and the centrifuging time are set to 5000r/min and 1 hour. The TEM image of Ti 3C2TX nano-sheets is shown in fig. 1a and the AFM image is shown in fig. 1b, and it can be seen from the AFM image that the thickness of Ti 3C2TX nano-sheets is about 3.5 nm.
10Ml of the Ti 3C2TX nanometer sheet solution is taken, 100 mg of melamine and 100 mg of triphenylphosphine are added in sequence, and the mixture is stirred until the mixture is uniform.
Adding tetrachloroauric acid solution into the solution, controlling the mass ratio of Au to Ti 3C2TX nanometer sheets to be 3%, and stirring for 30 minutes by a magnetic stirrer to uniformly mix the solution.
And freeze-drying the mixed solution.
And (3) annealing the mixture obtained by freeze drying in a tube furnace at normal pressure, wherein the annealing temperature and time are set to 500 ℃ and 2 hours by adopting argon protection. And after the annealing is finished, cooling to room temperature, and collecting a product to obtain the Au single-atom modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material.
Characterization of Au monoatomic modified three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite using a spherical aberration correction scanning transmission electron microscope, high magnification HAADF-STEM image (see fig. 6 a) shows that monoatomic Au is uniformly distributed on three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX. The three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX composite material modified by Au monoatoms is subjected to X-ray absorption fine spectrum characterization, and the FT-EXAFS spectrum (shown in figure 6 b) has only coordination peaks of Au, N and P and no Au-Au metal coordination peak, so that the Au is further proved to exist in a monoatomic form.
Example 6
Preparation of an Ir monatomic modified three-dimensional porous nitrogen-sulfur doped Ti 3C2TX composite material (abbreviated as Ir SA-PNSM):
Firstly, 1.2 g of lithium fluoride is added into 9mol/L hydrochloric acid solution, and the mixture is stirred and mixed uniformly. 1 g of Ti 3AlC2 was then added to the above solution in portions. After stirring for 1 hour until the mixture was uniform, the mixed solution was transferred to a thermostatic water bath, and the reaction temperature and time were set at 35℃and 24 hours. After the reaction is finished, centrifugally collecting a solid product after the reaction, washing the solid product to be close to neutral by deionized water, and centrifugally collecting the washed solid product. Adding deionized water into the solid product, carrying out ultrasonic treatment for 1 hour under the protection of argon and ice water bath, centrifuging and collecting supernatant to obtain Ti 3C2TX nanometer sheet solution (about 5 mg/mL), wherein the centrifuging speed and the centrifuging time are set to 5000r/min and 1 hour. The TEM image of Ti 3C2TX nano-sheets is shown in fig. 1a and the AFM image is shown in fig. 1b, and it can be seen from the AFM image that the thickness of Ti 3C2TX nano-sheets is about 3.5 nm.
10 Milliliters of the Ti 3C2TX nanometer sheet solution is taken, 100 milligrams of melamine and 100 milligrams of thiourea are sequentially added, and the mixture is stirred until the mixture is uniform.
And adding chloroiridium hexahydrate solution into the solution, controlling the mass ratio of Ir to Ti 3C2TX nano-sheets to be 3%, and stirring for 30 minutes by using a magnetic stirrer to uniformly mix the solution.
And freeze-drying the mixed solution.
And (3) annealing the mixture obtained by freeze drying in a tube furnace at normal pressure, wherein the annealing temperature and time are set to 500 ℃ and 2 hours by adopting argon protection. And after the annealing is finished, the temperature is reduced to room temperature, and the product is collected, so that the Ir single-atom modified three-dimensional porous nitrogen-sulfur doped Ti 3C2TX composite material can be obtained.
Characterization of the three-dimensional porous nitrogen-sulfur doped Ti 3C2TX composite modified by Ir monoatoms using a spherical aberration correction scanning transmission electron microscope, high-power HAADF-STEM image (see FIG. 7 a) shows that Ir monoatoms are uniformly distributed on the three-dimensional porous nitrogen-phosphorus doped Ti 3C2TX. X-ray photoelectron spectroscopy (XPS) shows that Ir atoms are anchored to the Ti 3C2TX substrate by chemical bonds with N and S heteroatoms (see FIGS. 7b, c). The three-dimensional porous nitrogen-sulfur doped Ti 3C2TX composite material modified by Ir monoatoms is subjected to X-ray absorption fine spectrum characterization, and the FT-EXAFS spectrum (see figure 7 d) has only coordination peaks of Ir and N and S, and does not have Ir-Ir metal coordination peaks, so that the Ir is further proved to exist in a monoatomic form.
In summary, the patent discloses a three-dimensional porous Ti 3C2TX composite material modified by metal monoatoms and a preparation method thereof. The method skillfully combines the metal single atom with the three-dimensional porous bimetal doped MXenes, and has originality and advancement. The above-described application scenario and embodiments are not intended to limit the present invention, and any person skilled in the art may make various modifications and alterations without departing from the spirit and scope of the present invention, and the scope of the present invention is defined by the scope of the claims.
Claims (9)
1. A three-dimensional porous MXenes composite material modified by metal monoatoms is characterized in that a main body is a double non-metal doped MXenes nano sheet with a three-dimensional porous structure, and metal elements are anchored on the nano sheet in a monoatomic mode;
the preparation method of the metal monoatomic modified three-dimensional porous MXenes composite material comprises the following steps:
s1, stripping a Ti 3AlC2 material by adopting a lithium fluoride-hydrochloric acid mixed solution to obtain a few-layer Ti 3C2TX nano-sheet solution;
s2, sequentially adding melamine, triphenylphosphine or thiourea and corresponding metal precursors to be doped into the less-layer Ti 3C2TX nano-sheet solution, and then freeze-drying the mixture;
S3, annealing the freeze-dried mixture in a tube furnace at normal pressure, adopting argon protection, setting the temperature to be 400-600 ℃ and the time to be 1-4 hours, cooling to room temperature after the annealing is finished, and collecting a reaction product.
2. The three-dimensional porous mxnes composite material of claim 1, wherein the mxnes comprises but is not limited to one of Ti 3C2TX、Ti2CTX、Mo2CTX.
3. The three-dimensional porous mxnes composite material of claim 1 in which the pore size is between 5-20 microns with the doped non-metals being N and P or S.
4. The three-dimensional porous mxnes composite material of claim 1, wherein the metal monoatoms include, but are not limited to, one of Pt, ir, ru, pd, au.
5. The three-dimensional porous mxnes composite material of claim 1 in which the doping level of the monoatomic metal is between 0.5% and 5.0% by weight.
6. The three-dimensional porous mxnes composite material of claim 1 in which the metal monoatoms are sub-nanoscale in size and coordinate to the non-metal atoms N and P or S.
7. The method for preparing the metal monatomic modified three-dimensional porous MXenes composite material as claimed in claim 1, which is characterized by comprising the following steps:
s1, stripping a Ti 3AlC2 material by adopting a lithium fluoride-hydrochloric acid mixed solution to obtain a few-layer Ti 3C2TX nano-sheet solution;
s2, sequentially adding melamine, triphenylphosphine or thiourea and corresponding metal precursors to be doped into the less-layer Ti 3C2TX nano-sheet solution, and then freeze-drying the mixture;
S3, annealing the freeze-dried mixture in a tube furnace at normal pressure, adopting argon protection, setting the temperature to be 400-600 ℃ and the time to be 1-4 hours, cooling to room temperature after the annealing is finished, and collecting a reaction product.
8. The method according to claim 7, wherein the triphenylphosphine in step S2 is dissolved in t-butanol and sonicated for 30-60 minutes.
9. The method according to claim 7, wherein the ratio of the Ti3C2TX nanoplatelets to the melamine in the step S2 is 1:1-1:3, and the ratio of the Ti3C2TX nanoplatelets to the triphenylphosphine or thiourea is 1:1-1:3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111401690.8A CN114643072B (en) | 2021-11-24 | 2021-11-24 | Preparation method of metal single-atom modified three-dimensional porous MXenes composite material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111401690.8A CN114643072B (en) | 2021-11-24 | 2021-11-24 | Preparation method of metal single-atom modified three-dimensional porous MXenes composite material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114643072A CN114643072A (en) | 2022-06-21 |
CN114643072B true CN114643072B (en) | 2024-05-31 |
Family
ID=81991859
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111401690.8A Active CN114643072B (en) | 2021-11-24 | 2021-11-24 | Preparation method of metal single-atom modified three-dimensional porous MXenes composite material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114643072B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115074086B (en) * | 2022-07-14 | 2024-02-20 | 西北工业大学 | Zn-MOFs derived ZnO/C/Ti 3 C 2 Composite wave-absorbing material and preparation method thereof |
CN116754622B (en) * | 2023-08-14 | 2023-10-27 | 湖南大学 | Method for detecting 2-methyl isoborneol in water |
CN117504750B (en) * | 2024-01-04 | 2024-04-05 | 中国科学院合肥物质科学研究院 | Low Pt-loaded MXene-carbon nanotube aerogel film, and preparation method and application thereof |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000318332A (en) * | 1999-05-07 | 2000-11-21 | Fuji Photo Film Co Ltd | Manufacture of lithographic printing plate |
CN108516528A (en) * | 2018-04-12 | 2018-09-11 | 大连理工大学 | A kind of three dimensional composite structure and its universal synthesis method based on three-dimensional MXene |
CN110876954A (en) * | 2019-12-06 | 2020-03-13 | 东莞理工学院 | Foamed MXene/C3N4/metal composite electrocatalyst and preparation method thereof |
CN111286078A (en) * | 2018-12-07 | 2020-06-16 | 中国科学院大连化学物理研究所 | Flexible conductive MXene-based foam and preparation method thereof |
CN111359647A (en) * | 2020-03-17 | 2020-07-03 | 中国石油大学(北京) | Ultrathin carbon layer coated nitrogen-doped cross-linked hierarchical pore molybdenum carbide material and preparation thereof |
CN111430154A (en) * | 2020-03-20 | 2020-07-17 | 北京化工大学 | Self-supporting three-dimensional porous MXene electrode and preparation method and application thereof |
KR20200093216A (en) * | 2019-01-28 | 2020-08-05 | 한국화학연구원 | Method for preparing two-dimensional vanadium carbide for hydrogen-generating catalyst electrode |
CN111569919A (en) * | 2020-05-18 | 2020-08-25 | 湖南大学 | Molybdenum disulfide quantum dot modified molybdenum carbide/foamed nickel composite material, preparation method thereof and application thereof in electrocatalytic oxygen evolution |
WO2020170132A1 (en) * | 2019-02-19 | 2020-08-27 | King Abdullah University Of Science And Technology | Single atom catalyst having a two dimensional support material |
CN113083295A (en) * | 2021-04-28 | 2021-07-09 | 中南大学 | Three-dimensional grading porous composite material with high quality activity, preparation method and application thereof |
CN113481528A (en) * | 2021-07-05 | 2021-10-08 | 哈尔滨工业大学(深圳) | Composite catalyst and preparation method and application thereof |
CN113683092A (en) * | 2021-10-26 | 2021-11-23 | 中国民航大学 | Nitrogen-sulfur co-doped Ti3C2-MXene nanosheet and preparation method and application thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109317179B (en) * | 2018-10-22 | 2020-09-08 | 苏州大学 | Two-dimensional nitrogen-doped carbon-based titanium dioxide composite material, preparation method thereof and application thereof in degradation removal of organic pollutants in water |
-
2021
- 2021-11-24 CN CN202111401690.8A patent/CN114643072B/en active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000318332A (en) * | 1999-05-07 | 2000-11-21 | Fuji Photo Film Co Ltd | Manufacture of lithographic printing plate |
CN108516528A (en) * | 2018-04-12 | 2018-09-11 | 大连理工大学 | A kind of three dimensional composite structure and its universal synthesis method based on three-dimensional MXene |
CN111286078A (en) * | 2018-12-07 | 2020-06-16 | 中国科学院大连化学物理研究所 | Flexible conductive MXene-based foam and preparation method thereof |
KR20200093216A (en) * | 2019-01-28 | 2020-08-05 | 한국화학연구원 | Method for preparing two-dimensional vanadium carbide for hydrogen-generating catalyst electrode |
WO2020170132A1 (en) * | 2019-02-19 | 2020-08-27 | King Abdullah University Of Science And Technology | Single atom catalyst having a two dimensional support material |
CN110876954A (en) * | 2019-12-06 | 2020-03-13 | 东莞理工学院 | Foamed MXene/C3N4/metal composite electrocatalyst and preparation method thereof |
CN111359647A (en) * | 2020-03-17 | 2020-07-03 | 中国石油大学(北京) | Ultrathin carbon layer coated nitrogen-doped cross-linked hierarchical pore molybdenum carbide material and preparation thereof |
CN111430154A (en) * | 2020-03-20 | 2020-07-17 | 北京化工大学 | Self-supporting three-dimensional porous MXene electrode and preparation method and application thereof |
CN111569919A (en) * | 2020-05-18 | 2020-08-25 | 湖南大学 | Molybdenum disulfide quantum dot modified molybdenum carbide/foamed nickel composite material, preparation method thereof and application thereof in electrocatalytic oxygen evolution |
CN113083295A (en) * | 2021-04-28 | 2021-07-09 | 中南大学 | Three-dimensional grading porous composite material with high quality activity, preparation method and application thereof |
CN113481528A (en) * | 2021-07-05 | 2021-10-08 | 哈尔滨工业大学(深圳) | Composite catalyst and preparation method and application thereof |
CN113683092A (en) * | 2021-10-26 | 2021-11-23 | 中国民航大学 | Nitrogen-sulfur co-doped Ti3C2-MXene nanosheet and preparation method and application thereof |
Non-Patent Citations (4)
Title |
---|
"Heteroatom-Mediated Interactions between Ruthenium Single Atoms and an MXene Support for Efficient Hydrogen Evolution";Vinoth Ramalingam et al.;《Advanced Materials》;第31卷(第48期);摘要,第2页右栏第2段,SI实验部分 * |
"Precious-Metal-Free Electrocatalysts for Activation of Hydrogen Evolution with Nonmetallic Electron Donor: Chemical Composition Controllable Phosphorous Doped Vanadium Carbide MXene";Yeoheung Yoon et al.;《Advanced Functional Materials》;第29卷(第30期);摘要,第3、4节 * |
"Vacancy and N dopants facilitated Ti3+ sites activity in 3D Ti3-xC2Ty MXene for electrochemical nitrogen fixation";Yacheng Shi et al.;《Applied Catalysis B: Environmental》;第297卷;第2.2、3.1节 * |
"含氮的褶皱状mxene在锂硫电池上的应用研究";无;《电子元件与信息技术》;20180220;第2卷(第02期);22-27 * |
Also Published As
Publication number | Publication date |
---|---|
CN114643072A (en) | 2022-06-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN114643072B (en) | Preparation method of metal single-atom modified three-dimensional porous MXenes composite material | |
Xu et al. | 3D hierarchical carbon-rich micro-/nanomaterials for energy storage and catalysis | |
KR101640545B1 (en) | Production method of catalyst-graphitic carbon nitride-reduced graphene oxide composite, the composite produced thereby, and an electrode using the same | |
WO2019113993A1 (en) | Carbon nanotube and method for fabrication thereof | |
Zhu et al. | Further construction of MnO2 composite through in-situ growth on MXene surface modified by carbon coating with outstanding catalytic properties on thermal decomposition of ammonium perchlorate | |
Qian et al. | Surfactant-free hybridization of transition metal oxide nanoparticles with conductive graphene for high-performance supercapacitor | |
KR101024798B1 (en) | Method for producing compositions of nanoparticles on solid surfaces | |
KR101347789B1 (en) | method of preparing carbon nitride-graphene composites and the carbon nitride-graphene composites prepared by the same method | |
JP5860957B2 (en) | Method for producing graphene | |
KR101231006B1 (en) | Preparing method of Alloy Catalyst using Conductive polymer coating | |
Wang et al. | Influence of tunable pore size on photocatalytic and photoelectrochemical performances of hierarchical porous TiO2/C nanocomposites synthesized via dual-Templating | |
KR20130015719A (en) | A complex comprising a mesoporous silicon oxide and a graphene, and method for preparing the same | |
US20160060123A1 (en) | Producing graphene and nanoporous graphene | |
CN110624552B (en) | Preparation method of graphene nano metal composite material | |
Chen et al. | Ni and N co-doped MoCx as efficient electrocatalysts for hydrogen evolution reaction at all-pH values | |
Umek et al. | The influence of the reaction temperature on the morphology of sodium titanate 1D nanostructures and their thermal stability | |
CN112701303B (en) | Preparation method and application of carbon tube intercalation nitrogen-doped carbon-coated cobalt particle catalyst | |
KR101195869B1 (en) | Method for preparing porous fullerene using by catalytic combustion | |
Shah et al. | Electrostatically regulated ternary-doped carbon foams with exposed active sites as metal-free oxygen reduction electrocatalysts | |
WO2022178916A1 (en) | Carbon nanotube which uses alcohol solvent as carbon source, and preparation method therefor | |
CN111825070B (en) | In-situ hybridized coordination polymer derived porous flower-like Co 2 P 2 O 7 Preparation method of/C composite material | |
CN114100648A (en) | Synthetic method of ZnMo-MOF-derived carbon-coated molybdenum carbide | |
CN114059095A (en) | Method for preparing supported ruthenium metal cluster catalyst through coordination regulation and application | |
Laishram et al. | 2D transition metal carbides (MXenes) for applications in electrocatalysis | |
CN109616334B (en) | Preparation method of carbon-coated metal oxide nanodot-loaded graphene composite material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |